CN102320629A - Method for producing reagent grade sodium sulfate by using white carbon black mother solution - Google Patents

Method for producing reagent grade sodium sulfate by using white carbon black mother solution Download PDF

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Publication number
CN102320629A
CN102320629A CN201110295041A CN201110295041A CN102320629A CN 102320629 A CN102320629 A CN 102320629A CN 201110295041 A CN201110295041 A CN 201110295041A CN 201110295041 A CN201110295041 A CN 201110295041A CN 102320629 A CN102320629 A CN 102320629A
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sodium sulfate
white carbon
carbon black
obtains
black mother
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CN201110295041A
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CN102320629B (en
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周海波
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FUJIAN HAINENG ADVANCED MATERIAL CO LTD
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FUJIAN HAINENG ADVANCED MATERIAL CO LTD
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Abstract

The invention discloses a method for producing reagent grade sodium sulfate by using a white carbon black mother solution. The method comprises the following steps of: 1) removing a little amount of solid residue such as white carbon black and the like in the white carbon black mother solution by using a mixed cellulose micropore filtration membrane with thickness phi of less than or equal to 0.15 micron, and preliminarily purifying the white carbon black mother solution into a sodium sulfate solution; 2) treating the sodium sulfate solution obtained in the step 1) by using chelating resin to obtain a 5 to 6 percent pure sodium sulfate solution; 3) performing electrodialytic concentration on the 5 to 6 percent pure sodium sulfate solution obtained in the step 2) to obtain a 15 to 25 percent pure sodium sulfate solution; and 4) performing multi-effect evaporation on the 15 to 25 percent pure sodium sulfate solution obtained in the step 3) to obtain crystal, separating the crystal by using a centrifuge, drying the separated crystal at the temperature of 120 DEG C, and thus obtaining a finished product. The sodium sulfate product prepared by the method has the characteristics of low impurity content, high quality, low moisture content and the like, and is a high reagent grade sodium sulfate product.

Description

Utilize the method for the aquatic product SILVER REAGENT of WHITE CARBON BLACK mother liquor sodium sulfate
Technical field
The invention belongs to the sodium sulfate working method, especially belong to a kind of method of utilizing the aquatic product SILVER REAGENT of WHITE CARBON BLACK mother liquor sodium sulfate.
Background technology
SODIUM SULPHATE ANHYDROUS 99PCT is important inorganic chemical product, is mainly used in the manufacturing of Chemicals such as sodium sulphite, bubble flower alkali, caustic soda, water glass; In addition, also be widely used in industries such as nonferrous metallurgy, plating, papermaking, glass, cement, enamel, printing and dyeing, process hides, synthon, synthetic detergent and medicine, market demand is very big.Current; The production of technical grade SODIUM SULPHATE ANHYDROUS 99PCT is mainly by prepared such as the dissolving of the process of the nitre mud in the natural salt lake, filtration, evaporation, dryings; Owing to contain a large amount of calcium, magnesium, iron, chlorine plasma in the nitre mud in salt lake, make industrial sulphuric acid sodium product foreign matter content height through this method preparation, production cost is bigger; Technological improvement is also very complicated, has restricted the development of sodium sulfate industry.
Along with the development of national economy, the demand to SODIUM SULPHATE ANHYDROUS 99PCT on the industrial production is increasing, and is also increasingly high to the quality requirements of product, and active development is sought new energy-saving and cost-reducing and SODIUM SULPHATE ANHYDROUS 99PCT preparation method with low cost and seemed very urgent.
At present, oneself breaks through 1,500,000 tons world's year output of WHITE CARBON BLACK (chemical ingredients is a silicon-dioxide), about 1,000,000 tons of the output of sulfuric acid precipitation method production WHITE CARBON BLACK.WHITE CARBON BLACK mother liquor water major ingredient is a sodium sulfate, is about 5.0 ~ 6.0% but sodium sulphate content is low in the mother liquor water, concentrates manufacture like direct employing multiple-effect evaporator and uses sodium sulfate, because of energy consumption is too high, has no economic worth.Therefore WHITE CARBON BLACK mother liquor water dilution back is discharged by most white carbon black production producer, has not only polluted environment but also has wasted valuable sodium sulfate resource.If can the sodium sulfate that wherein is rich in be reclaimed, the sodium sulfate recyclable approximately 0.4 ton according to one ton of WHITE CARBON BLACK Chemicals of every production in the industrial production calculates nearly 400,000 tons of annual callable sodium sulfate.
Summary of the invention
The object of the present invention is to provide a kind of WHITE CARBON BLACK mother liquor water that utilizes to concentrate the method that supervisor comes production SILVER REAGENT sodium sulfate through purification and plastic resin treatment and electrodialysis.
The objective of the invention is to realize like this, the described method of utilizing the aquatic product SILVER REAGENT of WHITE CARBON BLACK mother liquor sodium sulfate comprises the steps: 1) WHITE CARBON BLACK mother liquor water obtains metabisulfite solution through rough purification; 2) metabisulfite solution is handled through resin and is obtained bright sulfur acid sodium solution (5-6%); 3) bright sulfur acid sodium solution (5-6%) concentrates through electrodialysis and obtains 15-25% bright sulfur acid sodium solution, preferred 20% bright sulfur acid sodium solution; 4) obtain crystal behind 15-25% (preferred 20%) the bright sulfur acid sodium solution multiple-effect evaporation, obtain finished product after the crystal separation drying.The sodium sulfate of the aquatic product higher-grade of WHITE CARBON BLACK mother liquor capable of using like this SILVER REAGENT.Product grade has improved, and obtains considerable profit in the enterprise.
Above-mentioned steps 1) rough purification refers to adopt the waste liquid secondary filter that contains sodium sulfate that the sulfuric acid precipitation legal system is equipped with WHITE CARBON BLACK, removes in the WHITE CARBON BLACK mother liquor water solid residues such as a spot of WHITE CARBON BLACK, obtains filtrating; Described filtration can adopt cellulose membrane to filter; As adopt cellulose mixture millipore filtration (Φ≤0.15 μ m); Owing at first use cellulose membrane to filter to WHITE CARBON BLACK mother liquor water; Removed the solid residues such as remaining WHITE CARBON BLACK in the WHITE CARBON BLACK mother liquor water, the purity of the feasible sodium sulfate of preparing is higher.
Above-mentioned steps 2) resin is the crosslinked functional high molecule material that one type of ability and high volence metal ion form polygamy position complex compound.The mechanism of resin adsorbing metal ions is function atom and the metals ion generation coordination reaction on the resin, forms the rock steady structure of similar small molecules inner complex, and the mechanism of ion exchange resin absorption is electrostatic interaction.Therefore, compare with ion exchange resin, the bonding force of resin and metals ion is stronger, and selectivity is also higher, can be widely used in aspects such as the recovery separation of each metal ion species, amino acid whose fractionation and hydrometallurgy, public pollution control.But resin is as adopting the blue harmful ion Ca in scientific and technological LSC-500 alpha-amino phosphonate resin and the LSC-100 amido carboxylic acid resin effective elimination salt solution that knows 2+, Mg 2+, Sr 2+Deng, make secondary brine satisfy the ionic membrane processing requirement fully.As can adopt the resin of following concrete model: title D401, CEC, Mmol/g (doing) 1.95, water cut % 52-58; The selective adsorption divalent-metal ion.Purify the metabisulfite solution that obtains through step 1) and obtain the bright sulfur acid sodium solution that percentage concentration is 5-6% through the resin processing.
Above-mentioned steps 2) the bright sulfur acid sodium solution (5-6%) that obtains concentrates through electrodialysis and obtains 20% bright sulfur acid sodium solution; Described electrodialysis refers to the potential difference to be impellent; Utilize the selection perviousness of ion-exchange membrane, with the technology of the water sepn of the salt of charged component and non-charged component.Can realize solution desalination, concentrate, technological process such as refining or purifying.It is that the metabisulfite solution of 5-6% concentrates through electrodialysis that to obtain percentage concentration be 20% bright sulfur acid sodium solution that the present invention makes percentage concentration through general electrodialytic technique; It is the ion-exchange membrane of NRE-212 that described ion-exchange membrane can adopt model; Actually operating pressure can be 0.5-about 3.0kg/cm2, and operating voltage, electric current 100-250V, 1-3A.
Above-mentioned steps 3) the 20% bright sulfur acid sodium solution that obtains obtains crystal through behind the multiple-effect evaporation, obtains finished product after the crystal separation drying.Described multiple-effect evaporation refers to steam that an evaporator evaporation is come out and introduces next vaporizer, utilizes the water in its hot heating fumigators of emitting that condenses, two or more than two series connection to make full use of the vapo(u)rization system of heat energy.And evaporation is meant " with the method for heating, make in the solution partial solvent gasification and remove, thereby improve the concentration of solution, promote the technological operation that solute is separated out ".
Advantage of the present invention: present method has been opened up a kind of effective way that obtains the sodium sulfate product, adopts the sodium sulfate product of present method preparation, has characteristics such as foreign matter content is few, quality is high, water content is little, is the sodium sulfate of higher-grade SILVER REAGENT.The sodium sulfate technical target of the product of the higher-grade SILVER REAGENT of present method preparation is referring to table l.
The project indicator The check data of present method preparing product The sodium sulfate national standard of SILVER REAGENT (GB/T 6009-2003)
Sodium sulfate, massfraction (%) 99.6 ≥99.3
Calcium ion, (%) Do not detect ≤0.1
Mg ion, (in Mg) are (%) Do not detect ≤0.1
Iron ion, (in Fe) massfraction (%) 0.0001 ≤0.002
Cl ions, (in Cl) massfraction (%) 0.001 ≤0.12
Moisture, massfraction (%) 0.05 ≤0.1
Whiteness (R457) (%) 90 ≥85
Because the raw material that present method adopts is equipped with the WHITE CARBON BLACK mother liquor water that is rich in sodium sulfate of WHITE CARBON BLACK for the sulfuric acid precipitation legal system; When reducing production costs, alleviated the problem of environmental pollution that the discharging of WHITE CARBON BLACK mother liquor water causes, production technique has environmental protection, energy-conservation characteristic.The weight percent content of sodium sulfate is 5%~6% in the said WHITE CARBON BLACK mother liquor water.
 
Embodiment
Content of the present invention combines following examples to do explanation further, but content of the present invention is not limited only to content related among the embodiment.
EXAMPLE l:
Utilize the method for the aquatic product SILVER REAGENT of WHITE CARBON BLACK mother liquor sodium sulfate, comprise the steps:
1) adopt cellulose mixture millipore filtration (Φ≤0.15 μ m), with solid residues such as a spot of WHITE CARBON BLACKs in the WHITE CARBON BLACK mother liquor water removal WHITE CARBON BLACK mother liquor water, rough purification is a metabisulfite solution; 2) get 4L metabisulfite solution that step 1) obtains and handle through resin that to obtain percentage concentration be 5.6% bright sulfur acid sodium solution; Resin adopts blue dawn of scientific and technological LSC-500 alpha-amino phosphonate resin; Its CEC is 1.95Mmol/g (doing), and water cut is 52-58%; 3) to be 5.6% bright sulfur acid sodium solution through electrodialysis concentrate the percentage concentration that step 2) obtains that to obtain percentage concentration be 20% bright sulfur acid sodium solution, and electrodialysis concentrates used ion-exchange membrane, and can to adopt model be the ion-exchange membrane of NRE-212; Actually operating pressure can be 2.0kg/cm2, operating voltage, electric current 220V, 2A; 4) percentage concentration that obtains of step 3) is to obtain crystal behind 20% the bright sulfur acid sodium solution multiple-effect evaporation, obtains finished product after making crystal separation, 120 ℃ of dryings with whizzer.The equipment that said multiple-effect evaporation adopts is the product that Jiangsu good safe evaporation crystallization equipment ltd produces; So just produce the sodium sulfate that obtains the higher-grade SILVER REAGENT, its product obtains like following table 1 data through detecting.Product grade has improved, and obtains considerable profit in the enterprise.
Table 1 detects data for product:
The project indicator The check data of present method preparing product The sodium sulfate national standard of SILVER REAGENT (GB/T 6009-2003)
Sodium sulfate, massfraction (%) 99.6 ≥99.3
Calcium ion, (%) Do not detect ≤0.1
Mg ion, (in Mg) are (%) Do not detect ≤0.1
Iron ion, (in Fe) massfraction (%) 0.0001 ≤0.002
Cl ions, (in Cl) massfraction (%) 0.001 ≤0.12
Moisture, massfraction (%) 0.05 ≤0.1
Whiteness (R457) (%) 90 ≥85
Can know that by table 1 numerical value the present invention utilizes WHITE CARBON BLACK mother liquor water can produce the sodium sulfate of SILVER REAGENT.
Test shows: 1t mother liquor water can be produced 0.3t SILVER REAGENT sodium sulfate, 1200 yuan/ton of costs, and SILVER REAGENT SODIUM SULPHATE ANHYDROUS 99PCT price reaches more than 3500 yuan/ton, produces 1kt SILVER REAGENT SODIUM SULPHATE ANHYDROUS 99PCT per year and can make a profit 2,300,000 yuan.

Claims (3)

1. method of utilizing the aquatic product SILVER REAGENT of WHITE CARBON BLACK mother liquor sodium sulfate; Comprise the steps: 1) employing Φ≤0.15 μ m cellulose mixture millipore filtration; With solid residues such as a spot of WHITE CARBON BLACKs in the WHITE CARBON BLACK mother liquor water removal WHITE CARBON BLACK mother liquor water, rough purification is a metabisulfite solution; 2) getting metabisulfite solution that step 1) obtains handles through resin and obtains the bright sulfur acid sodium solution that percentage concentration is 5-6%; 3) percentage concentration that step 2) obtains is that the bright sulfur acid sodium solution of 5-6% concentrates through electrodialysis and obtains the bright sulfur acid sodium solution that percentage concentration is 15-25%; 4) percentage concentration that obtains of step 3) is to obtain crystal behind the bright sulfur acid sodium solution multiple-effect evaporation of 15-25%, makes the sodium sulfate that obtains SILVER REAGENT after crystal separation, the 120 ℃ of dryings with whizzer.
2. the method for utilizing the aquatic product SILVER REAGENT of WHITE CARBON BLACK mother liquor sodium sulfate according to claim 1 is characterized in that resin adopts the alpha-amino phosphonate resin, and its CEC is 1.95Mmol/g (doing), and water cut is 52-58%.
3. the method for utilizing the aquatic product SILVER REAGENT of WHITE CARBON BLACK mother liquor sodium sulfate according to claim 1 and 2 is characterized in that it is the ion-exchange membrane of NRE-212 that electrodialysis concentrates used ion-exchange membrane employing model; Actually operating pressure is 2.0kg/cm2, and operating voltage, electric current are respectively 220V and 2A.
CN 201110295041 2011-10-08 2011-10-08 Method for producing reagent grade sodium sulfate by using white carbon black mother solution Expired - Fee Related CN102320629B (en)

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Cited By (9)

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CN102897773A (en) * 2012-11-22 2013-01-30 株洲兴隆化工实业有限公司 Preparation method of white carbon black, as well as white carbon black
CN103130249A (en) * 2012-11-11 2013-06-05 安徽金禾实业股份有限公司 Preparing method of crystallized sodium sulfate in liquid SO2 by means of sodium citrate
CN103482809A (en) * 2013-08-26 2014-01-01 厦门世达膜科技有限公司 Technology for realizing zero discharge of waste water caused by white carbon black production
CN103723736A (en) * 2013-12-25 2014-04-16 江苏久吾高科技股份有限公司 Resource recovery method in white carbon black production process
CN103896309A (en) * 2014-03-28 2014-07-02 南风化工集团股份有限公司 Production method of chemical agent anhydrous sodium sulfate
CN105293532A (en) * 2014-07-28 2016-02-03 李明雄 Calcium removal process for lithium chloride solution during production
FR3054542A1 (en) * 2016-07-27 2018-02-02 Ocp Sa PROCESS FOR PRODUCING SODIUM SULFATE FROM PHOSPHOGYPSIS
CN107814457A (en) * 2017-12-11 2018-03-20 广州叶林环保科技有限公司 A kind of carbon black leaches inorganic salt treatment evaporative crystallization technique
CN111233008A (en) * 2020-01-17 2020-06-05 淮安市井沅科技有限公司 Novel production process of storage battery-grade anhydrous sodium sulfate

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CN1608996A (en) * 2004-10-09 2005-04-27 温润宪 Method of separating sodium sulfate crystal from mirabilite mineral
CN1915823A (en) * 2006-08-23 2007-02-21 湖北宜化集团有限责任公司 Method for preparing sodium sulfate in high purity
US20100226840A1 (en) * 2009-03-06 2010-09-09 Solvay Chemicals, Inc. Removal of impurities in the production of crystalline sodium carbonate, bicarbonate, or sulfite

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CN1608996A (en) * 2004-10-09 2005-04-27 温润宪 Method of separating sodium sulfate crystal from mirabilite mineral
CN1915823A (en) * 2006-08-23 2007-02-21 湖北宜化集团有限责任公司 Method for preparing sodium sulfate in high purity
US20100226840A1 (en) * 2009-03-06 2010-09-09 Solvay Chemicals, Inc. Removal of impurities in the production of crystalline sodium carbonate, bicarbonate, or sulfite

Cited By (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103130249A (en) * 2012-11-11 2013-06-05 安徽金禾实业股份有限公司 Preparing method of crystallized sodium sulfate in liquid SO2 by means of sodium citrate
CN103130249B (en) * 2012-11-11 2015-03-11 安徽金禾实业股份有限公司 Preparing method of crystallized sodium sulfate in liquid SO2 by means of sodium citrate
CN102897773A (en) * 2012-11-22 2013-01-30 株洲兴隆化工实业有限公司 Preparation method of white carbon black, as well as white carbon black
CN102897773B (en) * 2012-11-22 2015-08-12 株洲兴隆新材料股份有限公司 A kind of preparation method of white carbon black and white carbon black
CN103482809A (en) * 2013-08-26 2014-01-01 厦门世达膜科技有限公司 Technology for realizing zero discharge of waste water caused by white carbon black production
CN103723736A (en) * 2013-12-25 2014-04-16 江苏久吾高科技股份有限公司 Resource recovery method in white carbon black production process
CN103723736B (en) * 2013-12-25 2015-11-11 江苏久吾高科技股份有限公司 A kind of method of resource reclaim in white carbon black production technique
CN103896309A (en) * 2014-03-28 2014-07-02 南风化工集团股份有限公司 Production method of chemical agent anhydrous sodium sulfate
CN105293532A (en) * 2014-07-28 2016-02-03 李明雄 Calcium removal process for lithium chloride solution during production
FR3054542A1 (en) * 2016-07-27 2018-02-02 Ocp Sa PROCESS FOR PRODUCING SODIUM SULFATE FROM PHOSPHOGYPSIS
WO2018021900A3 (en) * 2016-07-27 2018-03-15 Ocp Sa Method for producing sodium sulphate from phosphogypsum
US20190263668A1 (en) * 2016-07-27 2019-08-29 Ocp Sa Process for producing sodium sulphate from phosphogypsum
US10689261B2 (en) * 2016-07-27 2020-06-23 Ocp Sa Process for producing sodium sulphate from phosphogypsum
RU2753536C2 (en) * 2016-07-27 2021-08-17 ОуСиПи СА Method for obtaining sodium sulfate from phosphogypsum
CN107814457A (en) * 2017-12-11 2018-03-20 广州叶林环保科技有限公司 A kind of carbon black leaches inorganic salt treatment evaporative crystallization technique
CN111233008A (en) * 2020-01-17 2020-06-05 淮安市井沅科技有限公司 Novel production process of storage battery-grade anhydrous sodium sulfate

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